4-azo-1-phenyl-pyrazolone derivative-containing lakes as pigments

ABSTRACT

An azo lake of the formula ##STR1## in which ##STR2## R 1  =--OH or --NR 4  R 5 , R 2  = ##STR3## except the lake of the formula ##STR4## Such azo lakes are useful as pigments.

This is a Request for filing a continuation-in-part, application under 37 CFR 1.62 of prior application Ser. No. 08/078,798, filed on Jun. 16, 1993, now abandoned, which is a continuation of Ser. No. 07/610,715, filed on Nov. 6, 1990, now abandoned, which is a continuation of Ser. No. 07/449,483, filed on Dec. 11, 1989, now abandoned, which is a continuation of Ser. No. 07/303,015, filed on Jan. 30, 1989, now abandoned, which is a continuation of Ser. No. 07/099,826, filed on Sep. 23, 1987, now abandoned, which is a continuation of Ser. No. 06/934,762, filed on Nov. 25, 1986, now abandoned.

The invention relates to azo lakes of the formula ##STR5## in which ##STR6## R¹ =--OH or --NR⁴ R⁵, R² = ##STR7## and when R¹ =--NR⁴ R⁵ additionally H or carboxylate, alkyl, in particular methyl,

R³ = ##STR8## R⁴, R⁵ =H, alkyl, cycloalkyl, aralkyl, aryl, each of which hydrocarbon radical can be substituted,

Z, Z', Z"=carboxylate, sulphonate,

A, J, G, E, Q, X,=H, --CF₃, halogen, --NO₂,

--CN, R⁶, --OR⁶, --NR⁶ R⁷, --NH₂, --SO₂ NH₂, --SO₂ --

NR⁶ R⁷, --CONH₂, --CONR⁶ R⁷, --NHCOR⁶,

M=ammonium or metal,

n, o, p=0, 1, 2,

m=n+o+p and when R² =--COOH,

n+o+p+1, with the condition

1≦m≦3,

L=valency of M.

R⁶, R⁷ =alkyl, cycloalkyl aralkyl, aryl, each

of which hydrocarbon radical can be substituted, except the lake of the formula ##STR9## m stands preferably for 2, i.e. the anionic part underlying the lake has two carboxylate and/or sulphonate groups which are particularly preferably situated in D and R³.

Alkyl (R², R⁴, R⁵, R⁶, R⁷) preferably signifies C₁ -C₄ -alkyl, in particular methyl and ethyl.

Cycloalkyl (R⁴, R⁵, R⁶, R⁷) preferably signifies C₃ -C₇ -cycloalkyl, in particular cyclopentyl and cyclohexyl.

Aralkyl (R⁴, R⁵, R⁶, R⁷) preferably signifies phenyl-C₁ -C₄ -alkyl, in particular benzyl and phenethyl.

Aryl (R⁴, R⁵, R⁶, R⁷) preferably signifies phenyl and naphthyl.

Halogen (A, J, G, E, Q, X, Y) preferably signifies chlorine, bromine and fluorine.

D preferably stands for ##STR10## (In this and the following formulae, recurring symbols have the meanings and preferred meanings already indicated in the formula I).

A', J', G'=H, Cl, Br, --CH₃, --C₂ H₅, --OCH₃, --OC₂ H₅, --NO₂, --NHCOCH₃.

Further preferred meanings for D are: ##STR11##

Individual examples of radicals D are: ##STR12## R¹ preferably stands for --OH or --NH₂. R² has the following preferred meanings: ##STR13## and --CH₃ when R¹ =--NR⁴ R⁵. E'=H, Cl, Br, --CH₃, --C₂ H₅, --OCH₃, --OC₂ H₅, --NHCOCH₃, --NO₂.

R³ has the following preferred meaning: ##STR14## X'=H, --Cl, --Br, --CH₃, --C₂ H₅ ; Y'=H, --Cl, --Br, --OCH₃, --OC₂ H₅, ##STR15## p is preferably 1 and Z" preferably stands in the 2'-or 3'-position of the phenyl ring.

Individual examples of radicals R³ are: ##STR16##

By combining the afforementioned preferred radicals, particularly preferred dyestuffs are formed. The table below shows some of these combinations:

                  TABLE                                                            ______________________________________                                         D           R.sup.1   R.sup.2     R.sup.3                                      ______________________________________                                          ##STR17##  OH                                                                                        ##STR18##                                                                                  ##STR19##                                   "           NH.sub.2  "           "                                            "           OH                                                                                        ##STR20##  "                                            "           NH.sub.2  "           "                                            "           NH.sub.2  CH.sub.3    "                                             ##STR21##  OH                                                                                        ##STR22##  "                                            "           NH.sub.2  "           "                                            "           NH.sub.2  CH.sub.3    "                                             ##STR23##  OH                                                                                        ##STR24##  "                                            "           NH.sub.2  CH.sub.3    "                                            "           NH.sub.2                                                                                  ##STR25##  "                                            ______________________________________                                    

M preferably signifies an alkali metal (Na, K) or alkaline earth metal (Ba, Sr), manganese or ammonium. Particularly preferably M signifies calcium.

Mixtures of azo lakes of the formula I having different Ms, for example Ca and Sr, likewise have good properties. The azo lakes according to the invention can occur in different crystal modifications.

It has to be mentioned that the lakes according to the invention can in general contain greater or lesser amounts of ammonium or alkali metal ions from the synthesis, for example Na, K, Li.

The compounds of the formula I are prepared by methods described in the literature.

For instance, the iminopyrazolones of the formula I are obtained by reacting the corresponding hydrazines with dimeric acetonitrile or the corresponding β-keto-nitriles. The 3-arylpyrazolones can be obtained, inter alia, by condensing the corresponding benzoyl acetates or benzoyl aceramides with hydrazines. The reactions can take place not only in the strongly and weakly acid but also in the neutral and alkaline region.

To prepare the azo lakes of the formula I, amines of the formula ##STR26## can be diazotized and coupled onto compounds of the formula ##STR27## and the dyestuffs be converted into the desired metal salts, The reactions can be carried out in the presence of nonionic, anionic or cationic dispersants and/or with the addition of or in organic solvents.

To obtain certain primary properties, it is expedient to heat the coupling mixture for some time, if desired to the boil or under pressure to above 100° C.

Particularly readily processable products are obtained on subjecting the lakes, after coupling, as moist presscakes or as dried powders, to an aftertreatment with organic solvents such as pyridine, dimethylformamide, alcohols such as ethanol, methanol, isopropanol, butanol, toluene, xylene, glycol, glycol monomethyl ethers, glacial acetic acid, chlorobenzene, dichlorobenzene, nitrobenzene or mixtures thereof, if desired with water, at refluxing temperature or under pressure at elevated temperature or on milling the lakes, after coupling, in the presence of milling auxiliaries. Good results can also be obtained by aftertreating the products, suspended in water, the abovementioned organic solvents or mixtures of these with themselves or water, with ultrasound at room or elevated temperature.

The isolated lakes can be subjected to a thermal aftertreatment, for example to a drying at elevated temperature, preferably at 40° C. to 150° C., including spraydrying.

Compounds of the formula I are useful pigments. Particularly useful pigments are the alkaline earth metal or manganese lakes. These can also be prepared from the generally more readily soluble ammonium or alkali metal lakes. The pigments according to the invention are suitable in particular for colouring plastics. They give greenish yellow to reddish orange and brown colorations. Particularly noteworthy are polyolefines such as polyethylene and polypropylene and also polystyrene with butadiene, modified polystyrene, polycarbonate, polyvinyl chloride, ABS and polymer blends such as polycarbonate/ABS, polyphenylene oxide/styrene-butadiene, ethylenepropylenecopolymer/propylene and polycarbonate/polybutylene terephthalate.

The lakes have an excellent thermostability, solvent, water, plasticizer and migration fastness, high tinctorial strength and also very good light and weathering resistance. The pigments are also suitable for colouring paints, rubber, natural and synthetic resins, filament viscose rayon and cellulose ethers or esters, polyamides, polyurethanes, polyglycol terephthalates and polyacrylonitrile in the spinning bulk.

EXAMPLE 1

6.4 g of 1-amino-4-chloro-5-methylbenzene-2-sulphonic acid are dissolved in 55 ml of water with 5 ml of sodium hydroxide solution and are precipitated with 9.7 ml of concentrated hydrochloric acid. This is followed by cooling with ice down to 0°-5° C. and diazotizing by adding 6.8 ml of a 30% strength sodium nitrite solution.

The diazotization is added to a solution of 9.5 g of 1-(3'-sulphophenyl)-3-phenyl-5-pyrazolone in 55.4 ml of 25% strength sodium acetate solution. After the coupling has ended, the temperature is raised to 80° C. and 24 g of calcium chloride are added. An hour at 80° C. is followed by filtration with suction, washing, and drying at 80° C.

This gives 16 g of a strongly reddish yellow lake of the formula ##STR28##

EXAMPLE 2

7 g of 1-amino-3,4-dichlorobenzene-6-sulphonic acid are diazotized as described in Example 1. After the reaction has ended, 44 ml of water and 7.6 g of 1-(3'-suphophenyl)-3-methyl-5-iminopyrazolone are added to the reaction mixture, which is brought to pH 6-6.5 with 25% strength ammonia solution and stirred until the coupling has ended. This is followed by heating to 80° C., addition of 24 g of calcium chloride and subsequent stirring at 80° C. for one hour.

Removal of the resulting pigment by filtration with suction, washing with water and spray-drying gives 15 g of a greenish yellow lake of the formula ##STR29##

EXAMPLE 3

Following a procedure as described in Example 1, the aqueous presscake is dewatered in butanol, filtered off with suction, washed and dried at 50° C. This gives 15 g of a yellow lake.

EXAMPLE 4

The method of Example 3 is used to dewater the aqueous presscake in butanol, and the suspension obtained is treated with ultrasound, filtered off with suction, washed and dried at 50° C. This gives 13.2 g of a greenish yellow lake having improved dispersibility.

The methods of Examples 1-4 were used to prepare Examples 5-161 mentioned below.

    __________________________________________________________________________     Example                                                                             Diazo component                                                                              Coupling component  Me Shade                                __________________________________________________________________________     5    1-amino-3,4-dichloro-                                                                        1-(2'-sulphophenyl)-3-methyl-                                                                      Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          5-iminopyrazolone                                                acid                                                                      6    1-amino-3,4-dichloro-                                                                        1-(2'-chloro-5'-sulphophenyl)-                                                                     Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          3-methyl-5-iminopyrazolone                                       acid                                                                      7    1-amino-3,4-dichloro-                                                                        1-(2',5'-dichloro-4'-sulpho-                                                                       Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          phenyl)-3-methyl-5-iminopyrazolone                               acid                                                                      8    1-amino-3,4-dichloro-                                                                        1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          methyl-5-iminopyrazolone                                         acid                                                                      9    1-amino-3,4-dichloro-                                                                        1-(2',4'-dichloro-5'-sulpho-                                                                       Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          phenyl)-3-methyl-5-iminopyrazolone                               acid                                                                      10   1-amino-3,4-dichloro-                                                                        1-(4'-methyl-3'-sulphophenyl)-                                                                     Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          3-methyl-5-iminopyrazolone                                       acid                                                                      11   1-amino-3,4-dichloro-                                                                        1-(6'-methyl-3'-sulphophenyl)-                                                                     Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          3-methyl-5-iminopyrazolone                                       acid                                                                      12   1-amino-3,4-dichloro-                                                                        1-(4'-chloro-5'-methyl-2'-sulpho-                                                                  Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          phenyl)-3-methyl-5-iminopyrazolone                               acid                                                                      13   1-amino-3,4-dichloro-                                                                        1-(3'-sulphophenyl)-3-phenyl-5-                                                                    Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          iminopyrazolone                                                  acid                                                                      14   1-amino-3,4-dichloro-                                                                        1-(2'-sulphophenyl)-3-phenyl-5-                                                                    Ca.sup.2+                                                                         Reddish                                   benzene-6-sulphonic                                                                          iminopyrazolone        yellow                                    acid                                                                      15   1-amino-3,4-dichloro-                                                                        1-(2'chloro-5'-sulphophenyl)-3-                                                                    Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          phenyl-5-iminopyrazolone                                         acid                                                                      16   1-amino-3,4-dichloro-                                                                        1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          phenyl-5-iminopyrazolone                                         acid                                                                      17   1-amino-3,4-dichloro-                                                                        1-(3',4'-dichloro-6'-sulpho-                                                                       Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          phenyl)-3-phenyl-5-iminopyrazolone                               acid                                                                      18   1-amino-3,4-dichloro-                                                                        1-(4'-methyl-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          phenyl-5-iminopyrazolone                                         acid                                                                      19   1-amino-3,4-dichloro-                                                                        1-(4'-methyl-2'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          phenyl-5-iminopyrazolone                                         acid                                                                      20   1-amino-3,4-dichloro-                                                                        1-(4'-chloro-6'-methyl-2'-sulpho-                                                                  Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          phenyl)-3-phenyl-5-iminopyrazolone                               acid                                                                      21   1-amino-3,4-dichloro-                                                                        1-(2'-sulphophenyl)-3-phenyl-                                                                      Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          pyrazol-5-one                                                    acid                                                                      22   1-amino-3,4-dichloro-                                                                        1-(3'-sulphophenyl)-3-phenyl-                                                                      Ca.sup.2+                                                                         Yellowish                                 benzene-6-sulphonic                                                                          pyrazol-5-one          orange                                    acid                                                                      23   1-amino-3,4-dichloro-                                                                        1-(2'-chloro-5'-sulphophenyl-3-                                                                    Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          phenyl-pyrazol-5-one                                             acid                                                                      24   1-amino-3,4-dichloro-                                                                        1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   benzene-6-sulphonic                                                                          phenyl-pyrazol-5-one   yellow                                    acid                                                                      25   1-amino-3,4-dichloro-                                                                        1-(4'-chloro-2'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   benzene-6-sulphonic                                                                          phenyl-pyrazol-5-one   yellow                                    acid                                                                      26   1-amino-3,4-dichloro-                                                                        1-(2',4'-dichloro-5'-sulphophenyl)-                                                                Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          3-phenyl-pyrazol-5-one                                           acid                                                                      27   1-amino-3,4-dichloro-                                                                        1-(4'-methyl-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   benzene-6-sulphonic                                                                          phenyl-pyrazol-5-one   yellow                                    acid                                                                      28   1-amino-3,4-dichloro-                                                                        1-(6'-methyl-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   benzene-6-sulphonic                                                                          phenyl-pyrazol-5-one   yellow                                    acid                                                                      29   1-amino-3,4-dichloro-                                                                        1-(4'-chloro-5'-methyl-2'-sulpho-                                                                  Ca.sup.2+                                                                         Reddish                                   benzene-6-sulphonic                                                                          phenyl)-3-phenyl-pyrazol-5-one                                                                        yellow                                    acid                                                                      30   1-amino-3,4-dichloro-                                                                        1-(3'-sulphophenyl)-3-(4'-chloro-                                                                  Ca.sup.2+                                                                         Orange                                    benzene-6-sulphonic                                                                          phenyl)-pyrazol-5-one                                            acid                                                                      31   1-amino-3,4-dichloro-                                                                        1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   benzene-6-sulphonic                                                                          (4'-chlorophenyl)-pyrazol-5-one                                                                       yellow                                    acid                                                                      32   1-amino-3,4-dichloro-                                                                        1-(2',5'-dichloro-4'-sulphophenyl)-                                                                Ca.sup.2+                                                                         Yellow                                    benzene-6-sulphonic                                                                          3-(4'-chlorophenyl)-pyrazol-5-one                                acid                                                                      33   1-amino-3,4-dichloro-                                                                        1-(4'-methyl-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   benzene-6-sulphonic                                                                          (4'-chlorophenyl)-pyrazol-5-one                                                                       yellow                                    acid                                                                      34   1-amino-3,4-dichloro-                                                                        1-(4'-chloro-5'-methyl-2'-sulpho-                                                                  Ca.sup.2+                                                                         Reddish                                   benzene-6-sulphonic                                                                          phenyl)-3-(4'-chlorophenyl)-                                                                          yellow                                    acid          pyrizol-5-one                                               35   1-amino-3,4-dichloro-                                                                        1-(3'-sulphophenyl)-3-(4'-methoxy-                                                                 Ca.sup.2+                                                                         Brownish                                  benzene-6-sulphonic                                                                          phenyl)-pyrazol-5-one  yellow                                    acid                                                                      36   1-amino-3,4-dichloro-                                                                        1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Brownish                                  benzene-6-sulphonic                                                                          (4'-methoxyphenyl)-pyrazol-5-one                                                                      yellow                                    acid                                                                      37   1-amino-3,4-dichloro-                                                                        1-(2',5'-dichloro-4'-sulphophenyl)-                                                                Ca.sup.2+                                                                         Red-                                      benzene-6-sulphonic                                                                          3-(4'-methoxyphenyl)-pyrazol-5-one                                                                    brownish                                  acid                                 yellow                               38   1-amino-3,4-dichloro-                                                                        1-(4'-chloro-5'-methyl-2'-sulpho-                                                                  Ca.sup.2+                                                                         Red-                                      benzene-6-sulphonic                                                                          phenyl)-3-(4'-methoxyphenyl)-                                                                         brownish                                  acid          pyrazol-5-one          yellow                               39   1-amino-3,4-dichloro-                                                                        1-(3'-sulphophenyl)-3-(4'-nitro-                                                                   Ca.sup.2+                                                                         Orange                                    benzene-6-sulphonic                                                                          phenyl)-pyrazol-5-one                                            acid                                                                      40   1-amino-4-chloro-5-                                                                          1-(3'-sulphophenyl)-3-methyl-5-                                                                    Ca.sup.2+                                                                         Greenish                                  methyl-benzene-2-                                                                            iminopyrazolone        yellow                                    sulphonic acid                                                            41   1-amino-4-chloro-5-                                                                          1-(2'-sulphophenyl)-3-methyl-5-                                                                    Ca.sup.2+                                                                         Yellow                                    methyl-benzene-2-                                                                            iminopyrazolone                                                  sulphonic acid                                                            42   1-amino-4-chloro-5-                                                                          1-(2'-chloro-5'-sulphophenyl)-                                                                     Ca.sup.2+                                                                         Yellow                                    methyl-benzene-2-                                                         3-methyl-5-iminopyrazolone                                                          sulphonic acid                                                            43   1-amino-4-chloro-5-                                                                          1-(2',5'-dichloro-4'-sulphophenyl)-                                                                Ca.sup.2+                                                                         Greenish                                  methyl-benzene-2-                                                         3-methyl-5-iminopyrazolone                                                                        yellow                                                           sulphonic acid                                                            44   1-amino-4-chloro-5-                                                                          1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Greenish                                  methyl-benzene-2-                                                                            methyl-5-iminopyrazolone                                                                              yellow                                    sulphonic acid                                                            45   1-amino-4-chloro-5-                                                                          1-(2',4'-dichloro-5'-sulphophenyl)-                                                                Ca.sup.2+                                                                         Greenish                                  methyl benzene-2-                                                                            3-methyl-5-iminopyrazolone                                                                            yellow                                    sulphonic acid                                                            46   1-amino-4-chloro-5-                                                                          1-(4'-methyl-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Greenish                                  methyl benzene-2-                                                                            methyl-5-iminopyrazolone                                                                              yellow                                    sulphonic acid                                                            47   1-amino-4-chloro-5-                                                                          1-(6'-methyl-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Yellow                                    methyl benzene-2-                                                                            methyl-5-iminopyrazolone                                         sulphonic acid                                                            48   1-amino-4-chloro-5-                                                                          1-(4'-chloro-5'-methyl-2-sulpho-                                                                   Ca.sup.2+                                                                         Yellow                                    methyl benzene-2-                                                                            phenyl)-3-methyl-5-iminopyrazolone                               sulphonic acid                                                            49   1-amino-4-chloro-5-                                                                          1-(3'-sulphophenyl)-3-phenyl-5-                                                                    Ca.sup.2+                                                                         Yellow                                    methyl benzene-2-                                                                            iminopyrazolone                                                  sulphonic acid                                                            50   1-amino-4-chloro-5-                                                                          1-(2'-sulphophenyl)-3-phenyl-5-                                                                    Ca.sup.2+                                                                         Yellow                                    methyl benzene-2-                                                                            iminopyrazolone                                                  sulphonic acid                                                            51   1-amino-4-chloro-5-                                                                          1-(2'-chloro-5'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Yellow                                    methyl benzene-2-                                                                            phenyl-5-iminopyrazolone                                         sulphonic acid                                                            52   1-amino-4-chloro-5-                                                                          1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Yellow                                    methyl benzene-2-                                                                            phenyl-5-iminopyrazolone                                         sulphonic acid                                                            53   1-amino-4-chloro-5-                                                                          1-(3',4'-dichloro-6'-sulphophenyl)-                                                                Ca.sup.2+                                                                         Yellow                                    methyl benzene-2-                                                                            3-phenyl-5-iminopyrazolone                                       sulphonic acid                                                            54   1-amino-4-chloro-5-                                                                          1-(4'-methyl-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   methyl benzene-2-                                                                            phenyl-5-iminopyrazolone                                                                              yellow                                    sulphonic acid                                                            55   1-amino-4-chloro-5-                                                                          1-(4'-methyl-2'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   methyl benzene-2-                                                                            phenyl-5-iminopyrazolone                                                                              yellow                                    sulphonic acid                                                            56   1-amino-4-chloro-5-                                                                          1-(4'-chloro-6'-methyl-2'-sulpho-                                                                  Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             phenyl)-3-phenyl-5-iminopyrazolone                                                                    yellow                                    sulphonic acid                                                            57   1-amino-4-chloro-5-                                                                          1-(2'-sulphophenyl-3-phenyl-                                                                       Ca.sup.2+                                                                         Yellowish                                 methylbenzene-2-                                                                             pyrazol-5-one          orange                                    sulphonic acid                                                            58   1-amino-4-chloro-5-                                                                          1-(2'-chloro-5'-sulphophenyl)-                                                                     Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             3-phenyl-pyrazol-5-one yellow                                    sulphonic acid                                                            59   1-amino-4-chloro-5-                                                                          1-(4'-chloro-3'-sulphophenyl)-                                                                     Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             3-phenyl-pyrazol-5-one yellow                                    sulphonic acid                                                            60   1-amino-4-chloro-5-                                                                          1-(4'-chloro-2'-sulphophenyl)-                                                                     Ca.sup.2+                                                                         Yellow                                    methylbenzene-2-                                                                             3-phenyl-pyrazol-5-one                                           sulphonic acid                                                            61   1-amino-4-chloro-5-                                                                          1-(2',4'-dichloro-5'-sulphophenyl)-                                                                Ca.sup.2+                                                                         Yellow                                    methylbenzene-2-                                                          3-phenyl-pyrazol-5-one                                                              sulphonic acid                                                            62   1-amino-4-chloro-5-                                                                          1-(4'-methyl-3'-sulphophenyl)-                                                                     Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             3-phenyl-pyrazol-5-one yellow                                    sulphonic acid                                                            63   1-amino-4-chloro-5-                                                                          1-(6'-methyl-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             phenyl-pyrazol-5-one   yellow                                    sulphonic acid                                                            64   1-amino-4-chloro-5-                                                                          1-(4'-chloro-5'-methyl-2'-sulpho-                                                                  Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             phenyl)-3-phenyl-pyrazol-5-one                                                                        yellow                                    sulphonic acid                                                            65   1-amino-4-chloro-5-                                                                          1-(3'-sulphophenyl)-3-(4'-chloro-                                                                  Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             phenyl)-pyrazol-5-one  yellow                                    sulphonic acid                                                            66   1-amino-4-chloro-5-                                                                          1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             (4'-chlorophenyl)-pyrazol-5-one                                                                       Yellow                                    sulphonic acid                                                            67   1-amino-4-chloro-5-                                                                          1-(2',5'-dichloro-4'-sulphophenyl)-                                                                Ca.sup.2+                                                                         Yellow                                    methylbenzene-2-                                                                             3-(4'-chlorophenyl)-pyrazol-5-one                                sulphonic acid                                                            68   1-amino-4-chloro-5-                                                                          1-(4'-methyl-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             (4'-chlorophenyl)-pyrazol-5-one                                                                       yellow                                    sulphonic acid                                                            69   1-amino-4-chloro-5-                                                                          1-(4'-chloro-5'-methyl-2'-sulpho-                                                                  Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             phenyl)-3-(4-chlorophenyl)-                                                                           yellow                                    sulphonic acid                                                                               pyrazol-5-one                                               70   1-amino-4-chloro-5-                                                                          1-(3'-sulphophenyl)-3-(4'-methoxy-                                                                 Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             phenyl)-pyrazol-5-one  yellow                                    sulphonic acid                                                            71   1-amino-4-chloro-5-                                                                          1-(4'-chloro-3'-sulphophenyl)-                                                                     Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             3-(4'-methoxyphenyl)-pyrazol-5-one                                                                    yellow                                    sulphonic acid                                                            72   1-amino-4-chloro-5-                                                                          1-(2',5'-dichloro-4'-sulpho-                                                                       Ca.sup.2+                                                                         Reddish                                   methylbenzene-2-                                                                             phenyl)-3-(4'-methoxyphenyl)-                                                                         yellow                                    sulphonic acid                                                                               pyrazol-5-one                                               73   1-amino-4-chloro-5-                                                                          1-(4'-chloro-5'-methyl-2'-sulpho-                                                                  Ca.sup.2+                                                                         Red-                                      methylbenzene-2-                                                                             phenyl)-3-(4'-methoxyphenyl)-                                                                         brownish                                  sulphonic acid                                                                               pyrazol-5-one          yellow                               74   1-amino-4-chloro-5-                                                                          1-(3'-sulphophenyl)-3-(4'-nitro-                                                                   Ca.sup.2+                                                                         Orange                                    methylbenzene-2-                                                                             phenyl)-pyrazol-5-one                                            sulphonic acid                                                            75   1-amino-2-chloro-                                                                            1-(3'-sulphophenyl)-3-methyl-5-                                                                    Ca.sup.2+                                                                         Yellow                                    benzene-5-sulphonic                                                                          iminopyrazolone                                                  acid                                                                      76   1-amino-2-chloro-                                                                            1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Yellow                                    benzene-5-sulphonic                                                                          methyl-5-iminopyrazolone                                         acid                                                                      77   1-amino-2-chloro-                                                                            1-(2'-chloro-5'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Yellow                                    benzene-5-sulphonic                                                                          methyl-5-iminopyrazolone                                         acid                                                                      78   1-amino-2-chloro-                                                                            1-(2',5'-dichloro-4'-sulpho-                                                                       Ca.sup.2+                                                                         Yellow                                    benzene-5-sulphonic                                                                          phenyl)-3-methyl-5-iminopyrazolone                               acid                                                                      79   1-amino-2-chloro-                                                                            1-(3'-sulphophenyl)-3-phenyl-5-                                                                    Ca.sup.2+                                                                         Yellow                                    benzene-5-sulphonic                                                                          iminopyrazolone                                                  acid                                                                      80   1-amino-2-chloro-                                                                            1-(2'-sulphophenyl)-3-phenyl-                                                                      Ca.sup.2+                                                                         Reddish                                   benzene-5-sulphonic                                                                          pyrazol-5-one          yellow                                    acid                                                                      81   1-amino-2-chloro-                                                                            1-(3'-sulphophenyl)-3-phenyl-                                                                      Ca.sup.2+                                                                         Reddish                                   benzene-5-sulphonic                                                                          pyrazol-5-one          yellow                                    acid                                                                      82   1-amino-2-chloro-                                                                            1-(2'-chloro-5-sulphophenyl)-3-                                                                    Ca.sup.2+                                                                         Yellow                                    benzene-5-sulphonic                                                                          phenyl-pyrazol-5-one                                             acid                                                                      83   1-amino-2-chloro-                                                                            1-(4'-chloro-3'-sulphophenyl)-                                                                     Ca.sup.2+                                                                         Reddish                                   benzene-5-sulphonic                                                                          3-phenyl-pyrazol-5-one yellow                                    acid                                                                      84   1-amino-2-chloro-                                                                            1-(3'-sulphophenyl)-3-(4'-chloro-                                                                  Ca.sup.2+                                                                         Reddish                                   benzene-5-sulphonic                                                                          phenyl)-pyrazol-5-one  yellow                                    acid                                                                      85   1-amino-2-chloro-                                                                            1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   benzene-5-sulphonic                                                                          (4'-chlorophenyl)-pyrazol-5-one                                                                       yellow                                    acid                                                                      86   1-amino-2-chloro-                                                                            1-(2',5'-dichloro-4'-sulphophenyl)-                                                                Ca.sup.2+                                                                         Reddish                                   benzene-5-sulphonic                                                                          3-(4'-chlorophenyl)-pyrazol-5-one                                                                     yellow                                    acid                                                                      87   1-amino-2-chloro-                                                                            1-(3'-sulphophenyl)-3-(4'-methoxy-                                                                 Ca.sup.2+                                                                         Brownish                                  benzene-5-sulphonic                                                                          phenyl)-pyrazol-5-one  yellow                                    acid                                                                      88   1-amino-2-chloro-                                                                            1-(2',5'-dichloro-4'-sulpho-                                                                       Ca.sup.2+                                                                         Brownish                                  benzene-5-sulphonic                                                                          phenyl-3-(4'-methoxyphenyl)-                                                                          yellow                                    acid          pyrazol-5-one                                               89   1-amino-2-chloro-                                                                            1-(3'-sulphophenyl)-3-(4'-                                                                         Ca.sup.2+                                                                         Orange                                    benzene-5-sulphonic                                                                          nitrophenyl)-pyrazol-5-one                                       acid                                                                      90   2-methoxyaniline-5-                                                                          1-(3'-sulphophenyl)-3-methyl-5-                                                                    Ca.sup.2+                                                                         Yellow                                    sulphonic acid                                                                               iminopyrazolone                                             91   2-methoxyaniline-5-                                                                          1-(4' -chloro-3'-sulphophenyl)-                                                                    Ca.sup.2+                                                                         Yellow                                    sulphonic acid                                                                               3-methyl-5-iminopyrazolone                                  92   2-methoxyaniline-5-                                                                          1-(2'-chloro-5'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Yellow                                    sulphonic acid                                                                               methyl-5-iminopyrazolone                                    93   2-methoxyaniline-5-                                                                          1-(2',5'-dichloro-4'-sulphophenyl)-                                                                Ca.sup.2+                                                                         Yellow                                    sulphonic acid                                                                               3-methyl-5-iminopyrazolone                                  94   2-methoxyaniline-5-                                                                          1-(3'-sulphophenyl)-3-phenyl-5-                                                                    Ca.sup.2+                                                                         Reddish                                   sulphonic acid                                                                               iminopyrazol-5-one     yellow                               95   2-methoxyaniline-5-                                                                          1-(2'-sulphophenyl)-3-phenyl-                                                                      Ca.sup.2+                                                                         Reddish                                   sulphonic acid                                                                               pyrazol-5-one          yellow                               96   2-methoxyaniline-5-                                                                          1-(3'-sulphophenyl)-3-phenyl-                                                                      Ca.sup.2+                                                                         Reddish                                   sulphonic acid                                                                               pyrazol-5-one          yellow                               97   2-methoxyaniline-5-                                                                          1-(2'-chloro-5'-sulphophenyl)-                                                                     Ca.sup.2+                                                                         Yellow                                    sulphonic acid                                                                               3-phenyl-pyrazol-5-one                                      98   2-methoxyaniline-5-                                                                          1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Strongly                                  sulphonic acid                                                                               phenyl-pyrazol-5-one   reddish                                                                        yellow                               99   2-methoxyaniline-5-                                                                          1-(3'-sulphophenyl)-3-(4'-chloro-                                                                  Ca.sup.2+                                                                         Reddish                                   sulphonic acid                                                                               phenyl)-pyrazol-5-one  yellow                               100  2-methoxyaniline-5-                                                                          1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   sulphonic acid                                                                               (4'-chlorophenyl)-pyrazol-5-one                                                                       yellow                               101  2-methoxyaniline-5-                                                                          1-(2',5'-dichloro-3'-sulphophenyl)-                                                                Ca.sup.2+                                                                         Reddish                                   sulphonic acid                                                                               3-(4'-chlorophenyl)-pyrazol-5-one                                                                     yellow                               102  2-methoxyaniline-5-                                                                          1-(3'-sulphophenyl)-3-(4'-methoxy-                                                                 Ca.sup.2+                                                                         Red-                                      sulphonic acid                                                                               phenyl)-pyrazol-5-one  brownish                                                                       yellow                               103  2-methoxyaniline-5-                                                                          1-(2',5'-dichloro-4'-sulpho-                                                                       Ca.sup.2+                                                                         Brownish                                  sulphonic acid                                                                               phenyl)-3-(4'-methoxyphenyl)-                                                                         yellow                                                  pyrazol-5-one                                               104  2-methoxyaniline-5-                                                                          1-(3'-sulphophenyl)-3-(4'-nitro-                                                                   Ca.sup.2+                                                                         Orange                                    sulphonic acid                                                                               phenyl)-pyrazol-5-one                                       105  4-methoxyaniline-                                                                            1-(3'-sulphophenyl)-3-methyl-5-                                                                    Ca.sup.2+                                                                         Reddish                                   2-sulphonic acid                                                                             iminopyrazolone        yellow                               106  4-methoxyaniline-                                                                            1-(4'-chloro-3'-sulphophenyl)-                                                                     Ca.sup.2+                                                                         Reddish                                   2-sulphonic acid                                                                             3-methyl-5-iminopyrazolone                                                                            yellow                               107  4-methoxyaniline-                                                                            1-(3'-sulphophenyl)-3-phenyl-5-                                                                    Ca.sup.2+                                                                         Reddish                                   2-sulphonic acid                                                                             iminopyrazolone        yellow                               108  4-methoxyaniline-                                                                            1-(2'-sulphophenyl)-3-phenyl-                                                                      Ca.sup.2+                                                                         Orange                                    2-sulphonic acid                                                                             phenyl-pyrazol-5-one                                        109  4-methoxyaniline-                                                                            1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   2-sulphonic acid                                                                             pyrazol-5-one          orange                               110  4-methoxyaniline-                                                                            1-(3'-sulphophenyl)-3-phenyl-                                                                      Ca.sup.2+                                                                         Orange                                    2-sulphonic acid                                                                             pyrazol-5-one                                               111  4-methoxyaniline-                                                                            1-(2',5'-dichloro-3'-sulphophenyl)-                                                                Ca.sup.2+                                                                         Yellowish                                 2-sulphonic acid                                                                             3-(4'-chlorophenyl)-pyrazol-5-one                                                                     orange                               112  1-amino-3-chloro-4-                                                                          1-(3'-sulphophenyl)-3-methyl-5-                                                                    Ca.sup.2+                                                                         Yellow                                    methylbenzene-6-                                                                             iminopyrazolone                                                  sulphonic acid                                                            113  1-amino-3-chloro-4-                                                                          1-(4'-chloro-3'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Yellow                                    methylbenzene-6-                                                                             phenyl-5-iminopyrazolone                                         sulphonic acid                                                            114  1-amino-3-chloro-4-                                                                          1-(2'-sulphophenyl)-3-phenyl-                                                                      Ca.sup.2+                                                                         Reddish                                   methylbenzene-6-                                                                             pyrazol-5-one          yellow                                    sulphonic acid                                                            115  1-amino-3-chloro-4-                                                                          I-(2'-chloro-5'-sulphophenyl)-3-                                                                   Ca.sup.2+                                                                         Reddish                                   methylbenzene-6-                                                                             (4'-chlorophenyl)-pyrazol-5-one                                                                       yellow                                    sulphonic acid                                                            116  1-amino-4-N-acetyl-                                                                          1-(3'-sulphophenyl)-3-methyl-5-                                                                    Ca.sup.2+                                                                         Yellow                                    amino-5-methoxybenzene-                                                                      iminopyrazolone                                                  2-sulphonic acid                                                          117  1-amino-4-N-acetyl-                                                                          1-(2'-sulphophenyl)-3-phenyl-                                                                      Ca.sup.2+                                                                         Reddish                                   amino-5-methoxybenzene-                                                                      pyrazol-5-one          yellow                                    2-sulphonic acid                                                          118  6-methoxy-4-nitro-                                                                           1-(3'-sulphophenyl)-3-methyl-                                                                      Ca.sup.2+                                                                         Reddish                                   aniline-3-sulphonic                                                                          5-iminopyrazolone      yellow                                    acid                                                                      119  6-methoxy-4-nitro-                                                                           1-(2'-sulphophenyl)-3-phenyl-                                                                      Ca.sup.2+                                                                         Orange                                    aniline-3-sulphonic                                                                          pyrazol-5-one                                                    acid                                                                      120  2-nitroaniline-4-                                                                            1-(3'-sulphophenyl)-3-methyl-5-                                                                    Ca.sup.2+                                                                         Yellow                                    sulphonic acid                                                                               iminopyrazolone                                             121  2-nitroaniline-4-                                                                            1-(2'-sulphophenyl)-3-phenyl-                                                                      Ca.sup.2+                                                                         Reddish                                   sulphonic acid                                                                               pyrazol-5-one          yellow                               __________________________________________________________________________

EXAMPLES 121-154

Furthermore, 1-amino-3-chloro-4-methylbenzene-6sulphonic acid was coupled onto the coupling components mentioned in Examples 5-15, 17-20, 22-39 by the methods indicated in Examples 1-4. Greenish yellow to reddish orange products are obtained.

EXAMPLES 155-161

4-ethoxyaniline-2-sulphonic acid was reacted with the coupling components mentioned in Examples 105-111 analogously to the methods in Examples 1-4. Reddish yellow to reddish orange pigments are obtained.

EXAMPLE 162

Transparent colouring of PVC-P:

0.1 part of yellow pigment prepared as described in Example 1 is mixed with 100 parts of PVC compound in a slow-speed laboratory mixing device, the mixture is discharged onto the running laboratory mixing rolls and homogenized, and drawn off as a sheet.

Yellow transparent colourings of excellent light stability are obtained.

EXAMPLE 163

Nontransparent colouring of PVC-P:

0.2 part of yellow pigment prepared as described in Example 42 are mixed together with 10 parts of titanium dioxide (futile type) with 100 parts of PVC compound and homogenized at 160° C. The sheet drawn off the laboratory mixing rolls has a nontransparent, yellow shade. The colourings have a very good migration and light fastness.

EXAMPLE 164

Translucent and nontransparent colourings of HD polyethylene and polypropylene:

100 parts of commercially available polyethylene granulate are mixed with 0.2 part of yellow pigment from Example 24 in a slow-speed mixing drum. The granulate obtained is homogenized at 170° C. via an extruder and drawn off to flat ribbons, which are granulated once more and injection-moulded on a screw injection moulding machine at a temperature above 200° C. On increasing the injection moulding temperature from 200° C. to 320° C. there is no observable change in colour.

Identical results are obtained with nontransparent colourings of titanium dioxide (rutile type) in HD-PE and in crystalline polypropylene, likewise as transparent and nontransparent pigmentations.

EXAMPLE 165

Colouring of polystyrene (PS) and butadiene-modified polystyrene (SB):

0.1 part of yellow pigment prepared as described in Example 65 is mixed with 0.5 part of titanium dioxide (rutile type) and 100 parts of PS granulate (SB granulate), and the mixture is injection-moulded on a screw injection moulding machine at elevated back pressure. Mouldings having a strongly reddish yellow, brilliant shade and uniform pigment distribution are obtained.

EXAMPLE 166

Colouring of ABS:

0.5 part of yellow pigment from Example 21 is mixed with 4 parts of titanium dioxide (rutile type) and 100 parts of ABS powder, the mixture is plasticized at 180° C. in an internal mixer, is discharged after homogenization via mixing rolls, and is granulated by the customary methods, and the granulate is injection-moulded on a screw injection moulding machine into mouldings having a luminous yellow colour. At processing temperatures of 220° C. to 280° C. and long residence times there are no observable changes in colour.

Similarly good results are obtained in plastics blends of the composition ABS/polycarbonate.

EXAMPLE 167

Colouring of polycarbonate (PC) and polycarbonate/polybutylene terephthalate (PC/PBT):

0.2 part of yellow pigment prepared as described in Example 2 is mixed dry with commercially available polycarbonate, the mixture is melted at 290° C. on a twin shaft extruder and in the course of melting the pigment is dispersed. The homogeneously coloured PC is granulated once more, and the granulate is processed by customary injection moulding methods at temperatures up to 340° C. There are no observable hue changes of the greenish yellow mouldings at different temperatures.

Even in PC/PBT the pigment is heat-resistant without change in shade at processing temperatures of 250° C. to 290° C., Also noteworthy is the excellent motor fuel resistance. 

We claim:
 1. An azo lake of the formula ##STR30## in which D represents ##STR31## in which A is Cl or CH₃ and J is H, Cl or CH₃, R¹ represents NH₂,R² represents C₁ -C₄ -alkyl, and R³ represents ##STR32## in which X is H or Cl and Y is H or Cl, and m=1+o+p with the condition 1≦m≦3, and o and p are 0, 1, or
 2. 2. An azo lake according to claim 1, wherein A and J are Cl.
 3. An azo lake according to claim 1, wherein A is Cl.
 4. An azo lake according to claim 1, wherein J is Cl.
 5. An azo lake according to claim 1, wherein either A or J is CH₃.
 6. An azo lake according to claim 1, of the formula ##STR33##
 7. An azo lake according to claim 1, wherein m is
 2. 